This application is a filing under 35 U.S.C. xc2xa7371 of PCT/EP99/06452, filed Sep. 2, 1999, which claims priority to German Application No. 198 40 195.7, filed Sep. 3, 1998.
1. The Field of the Invention
The present invention relates to main-chain polymers based on aromatic poly(1,3,4-heterodiazoles) which are suitable for use as the electroluminescent and/or electron-transport layer in optical devices, especially for light-emitting diodes (LEDs), and to a process for preparing them.
2. The Relevant Technology
The utilization of redox-active polymers and organic monomer compounds in optical devices is opening up the possibility of using simple processing techniques to realize large-area displays possessing low operating voltages and an emission over the entire spectral range, which it has not been possible to produce using the existing, conventional inorganic materials. Moreover, in contrast to the liquid-crystal displays, the electroluminescent displays are self-illuminating and therefore require no backlighting source.
Tang and van Slyke were the first to present LEDs based on organic materials (C. W. Tang, S. A. van Slyke; Appl. Phys. Lett. 51 (1987) 913). As a result it was possible to increase the luminescence efficiency relative to the inorganic materials and to produce LEDs which emit blue light. The organic multiple or single layers form sandwich structures between a transparent indium-tin oxide (ITO) anode and a metal cathode with a output function, such as Mg, Al or Ca, for example. With the structure of multiple layer systems consisting of electron-transport layer, emitter layer and hole-transport layer it was possible to increase the luminescence efficiency and its stability (C. Adachi, T. Tsutsui, S. Saito; App. Phys. Lett. 57 (1990) 531; Y. Hamada, C. Adachi, T. Tsutsui, S. Saito; Jpn. J. Appl. Phys. 31 (1992) 1812). Where monomers are used, the layers are realized by means of specific and hence costly vapour deposition techniques. The use of polymers permits a simplified structure of the device.
Conjugated polymers having semiconductor properties with energy gaps of between 3.5 and 1.0 eV, such as the mentioned poly(p-phenylenevinylene) (PPV) or poly-(p-phenylene) (PP), are used as emitters and/or hole-transport layers in the device structure of LEDs. It is necessary to synthesize organic-soluble materials in order to apply these polymers appropriately by means of processes that are simple to manage, such as spin coating or dipping, for example. One synthesis route is the preparation of soluble prepolymers which are converted into the corresponding insoluble conjugated polymers by a subsequent pyrolysis step.
Intense research work into PPV has been carried out, inter alia, by Friend et al. (A. B. Holmes, D. D. Bradley, A. R. Brown, P. L. Burn, R. H. Friend; Synthetic Metals 55-57 (1993) 4031, J. H. Burroughes, D. D. C. Bradley, R. H. Friend, EP 0423 283 B1) and by Hxc3x6rhold et al. (M. Helbig, H. H. Hxc3x6rhold; Makromol. Chem. 194 (1993) 1607; H. H. Hxc3x6rhold et al. DE 195 05 416 A1). Polymeric and oligomeric thiophenes have also been found to be particularly attractive. They permit the controlled adjustment of the wavelength of the light to be emitted, by variation of the substituents attached to the heterocycle (M. Granstrxc3x6m, M. Berggren and O. Inganxc3xa3s; Science 267 (1995) 1479; E. G. J. Staring et al.; Adv. Mater. 6 (1994) 934), although the quantum efficiency is unsatisfactory.
The structure of multilayer systems on a polymer basis makes it possible to increase considerably the efficiency of the emitting diodes. As additional layers which both improve the passage of the electrons through the layer and provide a barrier for holes, use has been made to date, inter alia, of side-chain polymers based on polymethacrylate with 1,3,4-oxadiazole groups in the side chain (X.-C. Li, F. Cacialli, M. Giles, J. Grxc3xcner, R. H. Friend, A. B. Holmes, St. C. Moratti, T. M. Yong, Adv. Mater. 7, 1995, 898) and copolymers with 1,3,4-oxadiazole units in the main chain (E. Buchwald, M. Meier, S. Karg, P. Pxc3x6sch, H.-W. Schmidt, P. Strohriegel, W. Riexcex2, M. Schwoerer, Adv. Mater. 7, 1995, 839, Q. Pei, Y. Yang, Adv. Mater. 7, 1995, 559).
Despite the enormous progress in the use of these materials in LEDs, the components still have limits with regard to service life, photostability, and stability to water and air.
It is an object of the present invention to provide polymers which possess electroluminescence properties and/or electron-transport properties and/or improvement with regard to the target profile of properties of the component as a whole, so that it can be used in illumination or display devices.
The invention provides aromatic poly(1,3,4-heterodiazoles) comprising aromatic poly(1,3,4-heterodiazole) comprising from 100 to 1,000 repeating units selected from the group consisting of 
in which R1, R2, R3 and R4 may be identical or different and are each an alkyl, alkoxy, phenyl, phenoxy or thiophenol group and X is S, O or N-phenyl.
One preferred class of the aromatic poly(1,3,4-heterodiazoles) of the invention has the general formula 
in which R1 and R2 are as defined above and n is an integer from 100 to 1,000.
As discussed above, the present invention provides aromatic poly(1,3,4-heterodiazoles) comprising aromatic poly(1,3,4-heterodiazole) comprising from 100 to 1,000 repeating units selected from the group consisting of 
in which R1, R2, R3 and R4 may be identical or different and are each an alkyl, alkoxy, phenyl, phenoxy or thiophenol group and X is S, O or N-phenyl.
One preferred class of the aromatic poly(1,2,4-heterodiazoles) of the invention has the general formula 
in which R1 and R2 are as defined above and n is an integer from 1 to 1,000.
As already mentioned, the substituents R1 to R4 may be alkyl groups. These generally have 1 to 18 carbon atoms, preferably up to 16 carbon atoms. Similar comments apply to the abovementioned alkoxy group.
The alkyl and alkoxy groups may be linear or branched, and it is preferred to select the substituents R1 and R2 and, if appropriate, R3 and R4 such that one of these radicals is branched while the other radical or radicals is or are linear.
The substituents R1, R2, R3 and R4 may also be abovementioned alkyl and alkoxy groups in which one or more non-adjacent CH2 groups have been replaced by xe2x80x94Oxe2x80x94or xe2x80x94Sxe2x80x94.
Furthermore, R1, R2, R3 and R4 may be a phenyl, phenoxy or thiophenol group.
The aromatic poly(1,3,4-heterodiazoles) of the invention are prepared by a process which is characterized in that equimolar amounts of an acid dichloride or two or more acid dichlorides, selected from the group consisting of 
in which R1, R2, R3 and R4 are as defined in claim 1, and of a dicarboxylic hydrazide or two or more dicarboxylic hydrazides, selected from the group consisting of 
in which R1, R2, R3 and R4 are as defined in claim 1, are subjected to a condensation polymerization, the condensation product is isolated, purified and then subjected to a ring-closure reaction in the presence of a water-withdrawing agent, and then the product is isolated and purified.
The water-withdrawing agent used is preferably phosphorus oxychloride.
Where sulphur or N-phenyl is to be introduced into the heterodiazole ring in place of oxygen, then aniline (to introduce N-phenyl) or phosphorus pentasulphide (to introduce sulphur) is added simultaneously during the ring-closure reaction. Solvents used are preferably benzene, toluene, xylene and 1,2-dichlorobenzene. The reaction temperature is preferably from 80 to 170xc2x0 C. and the reaction time is from 2 to 20 hours. The polymers obtained are isolated by precipitation from a non-solvent and may be purified by extraction, with alcohols, for example, or by further dissolution and precipitation from a non-solvent.
As already mentioned, the corresponding polyhydrazides are prepared by condensation in solution. Solvents used in this case are preferably benzene, toluene, xylene or 1,2-dichlorobenzene. The reaction temperature is preferably from 80 to 170xc2x0 C. and the reaction time is from 20 min to 5 h.
For the polycondensation, the corresponding acid dichloride or a mixture of acid dichlorides is dissolved in the aforementioned solvent or a mixture thereof, with heating, and the equimolar amount of one or more of the abovementioned acid dihydrazides in solution is added dropwise.
The condensation takes place judiciously by adding a basic catalyst, preferably pyridine.
The reactions are virtually quantitative. The condensation products obtained are isolated by precipitation, from alcohols, for example, and then purified by extraction with alcohols.
The preparation of the starting compounds takes place in accordance with methods known per se from the literature, such as those described, for example, in standard works on organic synthesis, e.g., Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, or in corresponding relevant journals.
For the synthesis of the thianthrene-containing 1,3,4-oxadiazole-containing polymer, for example, the required starting material is 3-phenoxythiophene-2,5-dicarboxylic acid, whose preparation is described in J. Org. Chem. 1982, 47, 1755-1759 (J. W. H. Watthey, M. Desai).
The polymers of the invention generally have from 100 to 1,000, preferably from 200 to 800, with particular preference from 300 to 700 repeating units.
The polymers of the invention are notable inter alia for high stability coupled with a high fluorescence quantum yield, these polymers emitting light in the blue region. Furthermore, on the basis of the 1,3,4-heterodiazole ring, they represent electron-accepting materials having very good barrier properties with regard to holes. The LUMO energies of the polymers provided fit very well with the output of the cathode materials, as has been determined by means of cyclovoltammetric measurements. This fact makes possible the efficient structure of multilayer arrangements.
The invention is based on the surprising finding that it is possible to adjust the electroluminescence by varying the layer thickness. Additionally it was supposed that the application of the aromatic poly(1,3,4-heterodiazoles) would reduce only the operating voltage of the device. As a complete surprise, however, the position of the recombination zone in a multilayer system is also changed in this way, so that the electroluminescence can be tailored by means of the polymeric layers of the invention, by choosing the layer thicknesses.
The heterodiazole-containing main-chain polymers of the invention may also be prepared, inter alia, in the form of layers and films in customary solvents and may therefore be used as electroluminescent and/or electron-transport layers in optical devices. The solubility in organic solvents of such rigid-chain, fully aromatic poly(1,3,4-heterodiazoles) has been achieved by introducing alkyl, alkoxy, thiophenol and/or phenoxy side groups into the polymeric main chain.
For their use as electroluminescent and electron-transport layers in optical devices, the synthesized polymers are applied by spin-coating or cast-on techniques to various solid substrates (ITO on glass substrates) and to flexible conductive polyethylene terephthalate films. The polymer layer thicknesses are between 40 and 500 nm (depending on the layer system) and must be optimized depending on the structure of the optical device.
For the realization of multiple-layer systems, a hole-transport layer is prepared first on the hole-injecting electrode, followed by the electron-transport layer, consisting of the polymers of the invention, atop it. This is followed by the application of an electron-injecting electrode, e.g., Ca, Mg, Al, In, Mg/Ag. The polymer materials used must be tailored to one another in such a way that, for example, mutual incipient dissolution is prevented. The production of injecting contacts is done by means of special multi-crucible resistance vaporization and DC or RF sputtering sources. Suitable hole-injecting electrode materials include those which possess a high output ( greater than 4.5 eV). They include gold, platinum, and indium-tin oxide (ITO) layers. The ITO layers (also available commercially: Balzers) must be designed by special vapour deposition techniques (RF sputtering) in such a way that they possess both high transparency ( greater than 80%) and a low surface resistance ( less than xcexaxcexa9/cm2). The typical layer thicknesses must therefore be between 80 and 150 nm.
In operation, electrodes are injected from the cathode into the electron-transport layer and, respectively, into the light-emitting layer. At the same time, holes are injected from the anode into the hole-transport layer and, respectively, directly into the light-emitting layer. Under the influence of the applied voltage, the charge carriers move towards one another through the active layers. At the interfaces between the charge-transport layers and the light-emitting layer, or directly in the light-emitting layer, respectively, electron/hole pairs are formed which recombine and, in doing so, emit light. The colour of the light emission can be varied, for example, by varying layer thicknesses in a multiple-layer system. The current/voltage characteristic lines and the optical properties (absorption, photoluminescence, electroluminescence) are measured after contacting the electrodes.